Electronic Coupling in C-Clamp-Shaped Molecules: Solvent-Mediated Superexchange Pathways

Abstract

Electron transfer (eT) rate constants are determined, in part, by the magnitude of donor (D)/acceptor (A) electronic coupling, {vert_bar}V{vert_bar}. When the D and A are separated beyond van der Waals contact, the intervening medium may mediate {vert_bar}V{vert_bar}. Herein, we report (1) electronic coupling mediated by fluid solvent in C-clamp-shaped D-S(pacer)-A molecules possessing well-defined D/A separations and orientations and (2) the dependence of {vert_bar}V{vert_bar} on solvent electronic structure. 27 refs., 1 tab.